Process for condensing vaporized metal halides



Aug, 3, p KRAUS PROCESS FOR GONDENSING VAPORIZED METAL HALIDES Filed April 3, 1946 Liqui Ti 0/ Gases Ti 01 ,00, etc.

10 Fe Cl fia/iz loflumauf INVENTOR.

ATTORNEY Patented Aug. 3, l 948 PROCESS FoacoNDENsING VAPORIZED, ,METAL muons Philip Berkeley Kraus; Chadds to E. I. du 'Pont de Nemours mington, Del'., a corporation Ford, Pa., assignor & Company, Wilof Delaware Application April a, 1946, Serial No. 659,412

This invention relates to the condensation of vaporized materials which normally condense to the solid rather than liquid state. More particu-Q larly, it relates to the condensation of'metallic halides, especially iron chlori'degfrom vaporous mixtures containing the chlorides or both titaniumandiron. Titanium tetrachloride is generally produced by reacting titanium-bearing materials; such as ilmenite ore, at elevated temperatures with ch rine, usually in the presence of a, reducing agent such as carbon, followed by volatilization of the titanium tetrachloride away from theresidual solid mixture. Most titanium-bearing materials employed in the process contain substantial amounts of iron, and as a result iron (ferric) chloride also forms and is volatilized during the chlorination. The gases leaving the reactor normally comprise titanium tetrachloride, ferric chloride, carbon monoxide, acted chlorine and minor, amounts of other metallic chlorides, including thoseof silicon or alu-j minum, If a mixture of chlorine with nitrogen rather than pure chlorine is employed in .the chlorination, large amounts of nitrogenz'also exist in the exhaust gases. As examples of typical, approximate'compositions of the reactor discharge gases from a chlorination process in which a mixture'of ilmenite and carbon is causedto be reacted with a chlorinating gas, the following tabulation is given;

Chlorinating Gas Chlorinating Gas i O H Case I I.

. Ch10ll[l(., 100% Chlorine 70%Nitmgen Titanium tetrachloride 33.5% by vol 10% by vol. Ferric chloride (as Fe;C1 9.8 b 2.9 by vol. Carbon dioxide 41. 12.3 by vol. Carbon monoxide 10.4 by vol 3.1 by vol. Chlorine 4.8 by vol 1.3 by vol. Nitrogen None. 70.4 by vol. Silicon tetrachlonde Slight amoun Slight amount.

luminum chloride .id ,Do.

The boiling points at atmospheric pressure of titanium tetrachloride and of ferric chloride are, respectively, 136.4 C. and 315 C. The temperatures at which ferric chloride commences to condense from the gas mixture-of the above type, i. e., the dewpoints thereof, are approximately 270 C. for case I and 250 C. for case II. The dewpoints for titanium tetrachloride in such mixture are approximately 100 C. and 65 C., respectively. The dewpoints for ferrous chloride, if

carbon dioxide, unre- 8 Claims. (Cl. 183-115) additional equipment plugging wherever the gas present, would be approximately 580 C. and530 0., respectively. These dewpointsrepresenttlie temperatures at which condensation begins, a1: though progressively lower temperatures are re quired for condensation as the concentration diminishes. For example, the dewpoints of mam: um and iron chlorides, present in a gas mixture to the extent of on percent, are, respectively; 15 C. and 230 C. e e

In spite of the considerable difference in vapor pressures of titanium tetrachloride and offerric chloride and the expectancy that their fractional separation through condensation might berela tivelysimple, the fractionalcondensation of their vaporized mixtures .has proved practicallyvery diificult, owing to the properties and haracter-f istics of ferric chloride. Thus, at temperatures below its boiling point ferric chloride is a solid and hence condenses directly to that state from the gas phase. In" conventional condensing apparatus the bulk of the cooling to eifect condensation takes place through thecondenser walls and the ferric chloride precipitates on such cool surfaces, tends to form a hard deposit thereon which is very difiicult to remove, reduces heat transfer through the apparatus walls, and even tually plugs up and causes shutdown of the apparatus, due to itsprogressive buildup on such walls. If the condensation occursfin the gas stream, fine particles of solid ferric chloride remain in suspension and are carried out of the condenser with the uncondensedtitanium tetrachloride gases. The presence of these suspended fine particles is very undesirable because they not only contaminate the titanium tetrachloride which is subsequently condensed, but they induce stream passesthrougharelatively narrow aper tureinthe apparatus. i e 1 Various expedientsdesigned to overcome such undesired plugging and'to provide a continuous type of chlorination operation have been 'pro posed by none has proved practically effective for the intended purpose, For instance, it has been proposed to overcome the involveddifiicul ties by condensing a substantial portion of the titanium tetrachloride with iron chloride to form a more fluid mass adapted to be removed from the condenser walls by mechanical means and to thereafter distill the titaniumtetrachloride out of the condensed iron chlorides. Another proposal is to condense the iron chloride inthe gas mixture, together with a substantial portion of the titanium tetrachloride, and to thereafter wash the vapor mixture containing a portionof without the attendant, objectionable plugging and apparatus stoppage arisin from ferric chic-- ride condensation which has characterized prior recovery methods. An additional, specific object is to effect separation of the iron chloride in the form of a dry powder which is substantially free from titanium tetrachloride and thereby avoid the necessity of separately treating the, iron chloride to recover further amounts of titanium tetrachloride. Additional objects and advantages of the invention will be apparent from the ensuing description and accompanying diagrammatic drawings in which:

low 300 0., which would induce ferric chloride Fig. I is .a vertical sectional view of one type of apparatus which can be used in practicing the invention.

The foregoing as well as other objects and advantages are attainable in this invention which broadly comprises subjecting a gaseous metal halide mixture to treatment with a sufficient amount of a vaporizable liquid cooling medium to, condense from said mixturesubstantially all of its halidecomponent which will condense to the solidphase while con-currently effectin substantially complete vaporization of said vaporizable liquid and then separating the condensed product from the residual gases.

In a more specific and preferred embodiment, the invention comprises rapidly dispersing suffis cient, cool liquid titanium tetrachloride throughout a gaseous mixture of ferric chloride and ti-. tanium tetrachloride during its passage through atreating zone as will efiect substantially com plete condensation in said zone of all the f rric chloride present in said mixture and ooncurrent- 1y with such condensation vaporizing substan tially all ofthe, liquid titanium tetrachloride employed in the treating and dispersingoperation,

then removing from said treating zone com densed ferric chloride produced therein,

In adapting the invention to practice, in ac cordance with such preferred embodiment and in, foi; example, an apparatus of the type shown I, ferric chloride-titanium tetrachloride gas mixtures of the approximate compositions shown in the above cases I and II (dependin on whether pure chlorine or a mixture of chlorine with nitrogen is used in their preparation) are fed, toav suitable condenser l via, a conduit 2 which is in open communication with a plurality of circumferentiallydisposedcondenser inlet ports 3 leading to the interior oi: said condenser. The gaseous mixtureso fed the condenser can be prepared by chlorinating titaniierous materials, such as i menite, rutile, orsimilar TiOz concentrates at elevated temperatures (600 C..- 1100? C.) in the presence of a solid or gaseousreducing agent, such as carbon, charcoal, coal, etc., and in accordance with known procedures. One useful and preferredmethod for yielding an an-. hydrous, metal chloride volatile at the tempera tureor formation compriSfis that disclosed i the 4 co-pending application of Robert M. McKinney, Serial No. 588,973, filed April 18, 1945. Among other useful methods those of U. S. Patents Nos. 1,179,394, 1,528,319, and 1,878,013 comprise suitable examples.

Prior to its treatment in accordance with the presentinventiomthe gaseous ferric chloride-titanium tetrachloride mixture from the reduction furnace is cooled in a suitable manner to a point substantially below the temperature at which it discharges from said furnace, but not below that necessary to maintain its ferric chloride content in vaporous state. Thus, the gaseous mixture may be cooled to below 600 0., and preferably to from about 400-500 C. (but not bedeposition). By such controlled coolin the necessity of utilizing an excess amount of liquid titanium tetrachloride in the subsequent fractional condensation is advantageously avoided.

After cooling, the gaseous mixture, .asalready stated, is introduced into the upper portion of the condenser I through the conduit 2 and ports 3-. Simultaneous with 'such introduction, liquid titanium tetrachlorideis. also fed via conduit .4 into, the upper portion .of the condenser and tangentially discharged or impinged, as shown, upon the surfaces of a disc or plate member 5 secured in fixed relationship to a shaft 6 and capable .of being rotated at a high rate of speed by means of an electric motor .or other driving means (not shown) By reason of the high speed of rotation of the disk element 5, the impinged: liquid TiCh is caused to be'immediately broken up into rela= tively fine, minute droplets, which quickly admix with and thoroughly disperse in the formof avery fine spray'or fog throughout. the gas mixture fed into the condenser through the conduit land ports 3. (Farev is exercised so that only an amourit of liquid TiCli is supplied to the rotating disc which will induce both rapid and complete cond'ensation of theiron chloride present in the gaseous mixture under treatment with simultaneous, concurrent. vaporizationin the zone of treatment of,the liquid T1014 fed th reinto. This exercise of control over the amount ofv liquid T1014 used in the condensation is of primary importance because unless it. is'observed, production of a dry ferric. chloride condensate free of TiC14 will not. result and all of the Ti li leaving the con will not be, inthe desired gaseous form. ,lTn-the latter event, an expensive treating operation to recover the T1014 from theiFeCla Will be required.

The amount of liquid titanium tetrachloride used to accomplish these results can be conveniently arrived at by calculating in accordance with the formula Lbs. of q cooling requisrsed in B. t. u.

the liquid tetrachloride necessary to reduce; the temperature of the gas mixture after mixing to from C.-200C., andpreferably in the range between C.-180 0., taking into account the latent heat of vaporization which is liberated by the, condensation, of iron chloride and that which is absorbed by the vaporization of; liquid titaniumtetrachloride. In. the caseof gas mixtures of the type, referred, to. above, thesamounts of liquid: ti-.- tanium-tetrachlorideat 18 C. required1per pound of titanium, tetrachloride in the gas mixtureare 1.6::poundsfor caserI and 2.4. poundsv for CaseII; Thesesfigures neglect. radiation losses from the condenser; and are given merely to, indicate-the orderof; magnitude of the. necessary addition of:

tion contemplated in my copending liquid 'I'iCli. The actual amountrequired'ior'any; particular. condenser system must bedetermined' on the basis of the temperature obtained after mixing and .obviously will vary with the composition and temperature ofwthe furnace gases introduced into the condenser, the temperature of the liquid TiCh, and the design anddegree of insulation ofthe condenser apparatus. i i After being subjectedto treatment withithe required amount of liquid titanium'tetrachloride, the treated gasespass downwardly through the treating zone 1, under the conical bafile members B'for discharge from the condenser. through the outlet 9. Condensed iron chloride which settles, out in the condenser collectsin the bottom thereof and is withdrawn therefrom, either; periodically or continuously, via condenser outlet-l0. i The fractionof the total. iron chlorides which thus settles out in the condenser is substantial in amount, butlwill vary witlr thecondenser design. Normally, however, and in thetype of condenser shown in Fig. I, which is provided with a conical bottom, more than 50% of the iron chloride fraction of the mixedgases will settle out for. removal. Condensed iron chloride which does not settle out is removed from the condenser with the gasstreamvia the outlet 9 for passage to suitable separatory apparatus, such as a cyclone separator (not shownlor the like. Care must be taken to maintain these gases at a temperature above thedew point for titanium tetrachloride during separation in the cyclone. For this purposeany duct work should be either heated'or well insulated and the separator itself should be maintained at temperatures ranging from about 140 C.-180 C. Separation in the cyclone willbe found to be greatly facilitated by reason of the fact that the condensed iron chloride iscompletely. dry so that there is little or no tendency for such condensate to stick to the internal walls ofthe separator. i

As a result of the above treatment, substantially all ofthe iron chloride present in the mix-; ture of1furnace gases fed to and treatedin'the' condenser is fractionally condensed and removed from such gases.- Should any smallamount of ferric chloride condensate remain in' the residual gases following such treatment; their substantially complete removal can be effected by-subjecting such residual gases to the stripping operaapplication Serial No. 659,411, filed April 3,1946; i

Advantageously the condensed ferric chloride formed as a result of my liquid TiClr treatment is in the form of a dry powder, substantially free from titanium tetrachloride and need not besub- Jected to the additional filtrations, distillations, etc., with their accompanying difficulties, heretofore required to recover residualTiCh from ferric chloride condensate. In addition, ferric chloride condensation takes place hereinalmo'st entirely out of contact with the Walls of the condenser, so that no tendency exists for deposits of such condensate to form and build up on the walls of the condenser and cause apparatus plugging andstoppage. As a result, "the invention affords a clean, economical, effective and continuous method for separating ironflchloride from gaseous, mixtures of that compound with titaniumtetra chloride. v

To a clearer understanding of the invention, the following specific example is given, which is merely illustrative and not to be considered as in limitation of theinvention: H

'Example nitrogen at room. temperature being admitted to the furnace perhour, to result in an exit gas;

II ofthe above table. tetrachloride and ferric chloride produced per hour was 1050 and523 pounds per hour. These gases were conveyed through ducts to a spray condenser of the type shown in Figure I, which was provided with a cylindrical section, a disc member rotating therein at 6000 R. P. M.,.:and,a

conical bottom inclined thirty degrees from the perpendicular. The gasesentered said condenser through a plurality of inlet ports and were at a temperature of. 400.Cj. i

2500 pounds per hourof liduid titanium retrachloride at ,18 0., containing 25 pounds of suspended iron chloride, were separately introduced into said, condenser anddirectly impinged upon a surface of said rapidly-rotating disc member, being thereupon converted into a fine spray. Dry, powdered ferric chloride resulting fromthe op-,

eration collected in the bottom of the condenser in an amount averaging 2'76 pounds per hour and was periodically removed therefrom. I

The gases leaving the condenser were at 0., contained on the average 28.0% by volume titanium tetrachloride, and immediately were introduced into a conventional type cyclone soparator externally heated to maintain the temperature of. the Walls between 1.60 1C. and 180: C., wherein 245 pounds of dry ferric chloride, substantially free from TiCll, per hour were separated. i The gases discharged from the cyclone were conveyedto a conventional type surface condenser wherein 96 per cent of the titanium tetra chloride was condensedby cooling to 27 C. This amounted to a yie1dof3350 pounds per hour. i

, While described as applied to certain preferred embodiments, the invention is not limited there-,-

to since variation therefrom may be resorted to;

without departing from its underlying principles and scope. Thus, though particularly useful in the separation of iron chloride from its gaseous mixtures with titanium tetrachloride, the condensation and separation is contemplated of that compound from other gaseous metal halide (especially chlorides) mixtures, such as of the metals tin, silicon, &c., which usually condense in the liquid phase and are more volatile than ferric, chloride. Also the inventionis applicable to separation of halides other than ironchloride which usually condense directlyto the solid state from vaporous mixtures with halides more vola tile than the halide condensing as a solid. For example, condensation and separation of ch10,- rides of chromium, zirconiumand aluminum may be eifected from mixture of these chlorides with more volatile halides such as the chlorides of tin, silicon, sulfur, &c. Again, while relatively pure liquid titanium tetrachloride comprises a preferred cooling medium, other liquid media at least as. volatile asvsaid chloride, which comasse ses forms of titanium tetrachloride may also be used, as can liquid TiCli containing a suspension of chloride; the-latter instance; the: ferricchloride in suspension is also obtained as a dry solicl' Riapiid dispersion ordistribution ot the cooling liquid throughout the gas mixture under" treat m'ent-ispreferably accomplished by the periph eral force exerted by the single: rotating disc'- member Alternatively, a plurality ofi these: disc membersor dispersing means, together with associatedmeans for impingingv the: liquid T5 6314= on the surfaces of each or all of said discs, mar be used. Similarly, any other meansfor efiecting the desired quiclcmixing and dispersal of the Tic-1'4 liquid throughout the gaseous mixtureentering the treating zone can be resorted to; such as one or more pressure spraying nozzles adapted to inject or atomizethe: liquid TiClie directly in the form of a fine spray or fogv into a high velocity stream of furnace gases;

Most efficient operation: of my process results when resort is bad to the relatively fine spray which results from impingementof liquid Ti'Clr enter a: rotating surface with: resulting intimate dispersion of the 'I iClr throughout the furnace gases. entering the-condenser; In such instance. at more intimate, quicker mixing is obtained and instantaneous cooling and rapid condensationof the iron chloride: takes place with simultaneous; complete vaporization of the liquid used! in the treating operation. The finely-divided l'iquid 'I i-Gli not only absorbs enough heat to condense the ironchloride, but also promotes formation ofi desired nuclei for promoting the condensaetion; As-a result, the condensed iron chloride is} the form of very finely-divided particles, and since a larger number of condensation nucleiform, the likelihood of liquid being occludedby condensed iron: chloride is considerably lessened. While such very fine spray use is preferred; it is: not essential; since the benefits of the invention: can be obtained even though the liquid tetra-- chloride should be admitted into the treating: zone in-relati v'ely large droplets, provided aquick mixing and: proper temperature control is exe'rted over the operation to eife'c't complete cond'e'nsation: of the iron chloride and siniult'a'lne'ous vaporization or all" the liquid TiCl r used the' treatment.

One oftlieprincipal advantages of the-inven tionresides' in the fact that all of the ferric" chloride condensed is obtained in theform of a dry powder substantially freefrom titanium tetrachloride. Consequently it is desirable that: means b'eprovided for separating" the iron chloride condensate fromthe gas stream, either by a suitably designed condenser, such as shown in Fig. I, by acyclone' s'eparator, by? a glass olotlr filter bag; or the like, or bya combination of" these means. Preferably; however, the gases leaving thecondenser are caused to pass directly to a condenser of' the type contemplated in my aforesaidcc-pe'n'ding application; wherein re moval of the ferric chloride in slurry form is enacted. 4

fcla'im as my invention 1. A process" for separating in the dry state a halide which condenses directly'tothe solidphase from its gaseous mixture with a more volatile metal halide, comprising treating said gaseous miitturewith a sufficient amount of a vapor iza-ble liquid cooling medium effect substantially complete condensation of" its solid' phase condensing component whilesimultaneousl varperizing. all: oil: said liquid nredium and men selia rating; the solid halide! condensate from: residual gaseousproductsa v I A process". for removing iron chloride in-the dry form from ai -gaseous mixture? with a more volatilem'etalr halide which: comprises: rapidly mixing; with: said gaseous mixture an amountlof liquid titanium tetrachlorid suillcient to dense. substantially all of the iron chloride: present said mixture while simultaneously vapor-' icing: allof. the liquid titanium: tetrachloride so employed: andi then separating the iron chloride condensate from the residual vaporous halide products. i

3=. process for removing an iron chloride 'ini the: dry form froma gaseous mixture withlaimore volatile metal halide which comprises rapidly-dis persingl suificientliquid titanium tetrachloride throughout said gaseous mixture to condense-sub stantially; allof' itsiron chloride content and aocompanying, simultaneous complete vaporizationv or the liquid TiCll so. employed, and then separating resulting. iron chloride condensate fromthe residual vaporous halide products; l

4*. process for removing ferric chloride in the dry form from. a gaseous mixture with a more volatile metal halide which comprises rapidly and mechanically dispersing in: said mixture an amount of liquid titanium tetrachloride sufficient to. condense substantiallyall of its ferric chloride: content while being simultaneously completely vaporized in the condensation process,.and senarating thecondensed ferric chloride from the residual gaseousvhalide.

5;- A process for removing. ferric chloride: in the dryforxrr from a gaseous mixturewith titanium tetrachloride: which comprises: mechanically dispersing throughout said gaseous mixture and in the form of fine. minute droplets, sufii'cient 'cool liquidtitanium tetrachloride to effect condense:-

tion of substantially all of the iron: chloride pres ent' in said mixture with concurrent. substantially complete vaporization of. the T1614. employed im the condensation, and: separating the ferric: chicridercondensate fromthegases so treated;

6. Aprocessfor removing: ferric chloridein the dry' form from a gaseous mixture with: titanium tetrachloridewhichi com-prisesintroducing saidgaseous mixture; whil at a temperature" ranging? from- 300-600P into a treating: zone; mechan ically, and: uniformly: dispersing throughout saidi gases in said treating. zone an amount of liquid? titanium tetrachloride which is sufiicient to effect, condensation of: substantially all of its ironchloride content and will be; simultaneously vat-- pori-zed' during the condensation, and: thereatt'en separating; the condensed ferric chloride from the gases-so treated; J r l I,

71A process for removing ferric chloride the: dry.- formfroma gaseous mixture with titannium-i tetrachloride which comprises introduce ing, said gaseous mixture, while at a temperature: ranging. from 400 (2.500 C., into a-treating zone mechanically. and uniforml dispersing throughoutsaidlgases insaid treating zone an amount of liquid titanium tetrachloride which issuificientto effect condensation of. all. of its iron chloride con tent and will be simultaneously vaporized during, the condensation, and thereafter separating the condensed" ferric chloride from the" gases so treated. H

8'". A process for removing iron chloride in dry form from a gaseousmixture containingga more volatile metal halide which comprises admixing with said gaseous mixture an amount of"sai*d= more volatile metal halide, in liquid form, which is not in excess of that required to effect eondensation of substantially all of the iron chloride present in said mixture while being simultaneously vaporized in the process, and separating the condensed iron chloride from the vaporous halide products.

PHILIP BERKELEY KRAUS.

REFERENCES CITED The following references are of record in the 1 file of this patent:

Number 

